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US3773487A - Fabrication and chemical tempering of vitreous products - Google Patents

Fabrication and chemical tempering of vitreous products Download PDF

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US3773487A
US3773487A US00723360A US72336068A US3773487A US 3773487 A US3773487 A US 3773487A US 00723360 A US00723360 A US 00723360A US 72336068 A US72336068 A US 72336068A US 3773487 A US3773487 A US 3773487A
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glass
ions
article
smaller
exchangeable
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E Plumat
Laethem R Van
F Toussaint
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S65/00—Glass manufacturing
    • Y10S65/15—Nonoxygen containing chalogenides

Definitions

  • ABSTRACT A process and apparatus for chemically tempering articles of glass or other vitreous or vitrocrystalline materials by replacing ions initially present in the surface layers of such article by smaller ions as the article is undergoing a primary forming operation while still in a molten or softened state.
  • the present invention relates to vitreous or vitrocrystalline products, and particularly to the chemical tempering of such products as they are undergoing their primary forming operation.
  • tempering In the fabrication of glass articles, for example glass sheets and hollow glass articles, it is current practice to temper such articles in order to improve their mechanical properties.
  • One well-known type of tempering is known as thermal tempering and is carried out by heating the article to a temperature close to its softening point and then rapidly cooling the article in a current of air.
  • a first type involves an exchange of ions between the glass and the communicating medium at a temperature which is sufficiently high to permit stress relaxation to occur in the glass, the ions penetrating into the glass being of such a type as to impart a reduced coefficient of thermal expansion to the glass surface layers. These ions are normally ofa smaller diameter than the ions which they replace in the glass.
  • ions initially present in the glass surface layers are replaced by ions having a larger diameter and the ion exchange is carried out while the glass surface layers are maintained at a temperature below the annealing point of the glass (corresponding to a viscosity of poises) so that substantial stress relaxation does not occur.
  • Thermal tempering of fabricated glass articles has certain serious disadvantages, notably in that there is a considerable risk that the articles will be deformed thereby. Moreover, thermal tempering can not be applied to thin glass sheets having a thickness of less than about 3 mm.
  • Another object of the invention is to substantially improve the results produced by chemical tempering processes.
  • Yet another object of the invention is to increase the depth of ion penetration in such processes.
  • a further object of the invention is to decrease the concentration gradient of ions diffused into the surface layers of glass and vitrocrystalline material articles.
  • Yet a further object of the invention is to substantially increase the mechanical strength of such articles.
  • a process for forming molten or softened glass into a shaped article which process includes carrying out a primary forming operation, of the improvement composed of bringing the glass, while it is still in the molten or softened state during the primary forming operation, into contact with an ionized medium constituting a source of ions which are of smaller diameter than at least one type of ions initially present in the glass, and permitting these smaller ions from the medium to diffuse into the glass, in regions which will constitute surface layers of the resulting article, in exchange for such ions initially present in the glass, such diffusion occurring before the glass has assumed its final form.
  • the objects according to the invention are also achieved by the provision of a glass body whose surface layers are compressively stressed by chemically tempering the body to cause ions initially present in the glass to be replaced by ions having a smaller diameter, and by the displacement of ions into and toward the interior of the body before it has assumed its final form.
  • the invention includes apparatus for forming molten or softened glass into a shaped article.
  • This apparatus essentially includes shaping means for subjecting the glass to a primary forming operation while it remains in its molten or softened state, and means associated with the shaping means for delivering an ionized medium, containing ions of smaller diameter than one type of ions initially present in the glass, into contact with the glass in the shaping means for permitting the smaller-diameter ions to replace the one type of ions in the glass before the glass has been formed into its final shape.
  • FIGURE of the drawings is a simplified, cross-sectional, elevational view of a portion of a drawing apparatus provided with one preferred embodiment of the present invention.
  • molten or plastic glass is, while it is being fashioned for the purpose of fabricating a sheet, band or other shaped article, placed in contact with an ionized medium furnishing ions of smaller diameter than larger ions originally present in the glass, which smaller ions replace the larger ions in order to cause a quantity of the smaller ions to penetrate into the glass portions which will form at least certain surface zones of the article, this penetration being effectuated before the glass has been given its final form.
  • Protons i.e. hydrogen atoms which have lost their electron, are to be considered in the group of smaller-diameter ions.
  • the invention is not, however, limited to the use of vitrifiable mixtures of ordinary soda-lime glass as the starting material. It should be appreciated that it is also possible to utilize vitrifiable mixtures of glass which, either spontaneously or as the result of a suitable subsequent treatment, undergo a certain crystallization so that the material becomes vitro-crystalline. However, for purposes of simplicity, the following description will be given with reference to articles made only of glass.
  • the invention can be advantageously applied to the construction of glass articles by pressing, blowing, or by any other primary fashioning, or forming, operation
  • the invention can be applied with particular advantage to the fabrication of products made from drawn glass, for example drawn glass ribbons which are to be cut into sheets, as well as fibers, strips and drawn tubes.
  • the ion exchange is preferably effectuated completely or principally while the glass is at a temperature above its softening point.
  • the softening point is at a temperature which is approximately equal to 1.15 times the annealing temperature of the material. In the case of ordinary soda-lime glasses, which were first mentioned above, the softening point is approximately equal to 620C.
  • the ion exchange begin at least when the glass is at a temperature above its mobility point.
  • the mobility point is here defined as being equal to 1.55 times the annealing temperature of the material. In the case of the above-mentioned sodalime glasses, the mobility point is around 840C.
  • the ion exchange between the glass and the medium in contact therewith preferably commences at least before and/or when glass attains the drawing meniscus.
  • Optimum results are obtained when the ion exchange is caused to take place either completely or in large measure before the glass leaves the meniscus.
  • the present invention offers several very important advantages. For example, it has been noted that the ions provided by the treatment medium penetrate more deeply into the glass than when the same glass was chemically tempered according to the prior-art processes. The improvement is both substantial and surprising. It appears to be due, at least to a certain extent, to the internal movement which is produced in the glass body after the smaller-diameter ions have penetrated therein. in addition, the penetration into the glass by the ions coming from the treatment medium has been found to be re markably uniform.
  • the invention also offers another important advantage.
  • a tempered glass article can be produced more easily and at lower cost when the tempering process according to the invention is used than when a prior-art chemical tempering process is used.
  • One reason for this is that the process according to the invention eliminates the need for costly reheating processes which, until the present, had of necessity to precede the ion exchange.
  • the article is tempered before being completely shaped.
  • the ion exchange which is carried out during the primary forming operation is an exchange of alkali metal ions.
  • it may involve an exchange of sodium ions initially present in the glass for lithium ions provided in the medium utilized for treating the glass.
  • Lithium ions present in lithium-containing glass can be replaced by protons.
  • the present invention makes it possible to produce sheets of tempered glass, for example vehicle Windshields, which, if they should break, will spontaneously divide into small noncutting fragments.
  • the invention can also be applied for producing tempered glass in the form of sheets having a thickness of less than 3 mm.
  • the ion exchange is effectuated between a medium serving to treat the glass and the molten medium flowing in and/or towards the meniscus in a drawing chamber, as will be described in greater detail below, the ions diffuse into the glass symmetrically with respect to the median plane of the drawn glass sheet. It is, however, possible to carry out the invention in such a manner as to produce compressive stresses only in one of the surfaces of the sheets.
  • the medium used for treating the glass can be liquid or gaseous. Examples of liquid mediums are a molten salt or a mixture of molten salts.
  • Gaseous mediums can be constituted by one or more salts, and preferably a nitrate, a sulphate, or a mixture of these two salts, which vaporize at a temperature below that at which the glass is to be treated.
  • the effect, when a gaseous medium is utilized, is slower than that observed when the medium is constituted by molten salts.
  • the glass treatment medium is constituted by one or more molten salts
  • a thin film of the medium serving to treat the glass can adhere thereto.
  • a thin film of the treating medium can be caused to adhere to the glass ribbon as it leaves the meniscus.
  • this coating can be accomplished by cooling the coating, for example by means of several coolers situated along the path of the ribbon or by blowing a cooling fluid against the coated ribbon.
  • the adherent film of the medium in question could also, in certain cases, be so thin that this special cooling is not necessary.
  • the adherent film could rest in place in order to protect the glass surfaces against any deterioration due to the action of gas currents present in the shaping machine.
  • the replacement of ions initially present in the glass by smaller-diameter ions during the course of the primary operation for forming the glass could be followed by a second ion exchange in which the ions introduced into the glass during the first ion exchange are replaced by larger-diameter ions.
  • Such larger-diameter ions could be, for example, the ions of the element which was replaced during the course of the first ion exchange.
  • the ions introduced into the glass in the second ion exchange are preferably of larger diameter than the ions of the glass which were replaced during the first ion exchange.
  • potassium, rubidium or cesium ions could be introduced in substitution for the lithium ions by the second ion exchange.
  • the larger-diameter ions could also be ions of an alkalineearth metal, such as calcium or magnesium.
  • the effect of the second ion exchange is to reinforce the glass article.
  • the second ion exchange can be, and preferably is, carried out during the cooling of the glass following the first ion exchange and after the glass has attained a temperature below its annealing point.
  • the quantity of ions penetrating into the glass per unit time during an ion exchange operation and the depth to which the ions penetrate in the glass depend, among other things, on the temperature and the concentration of the ions in the medium in contact with the glass.
  • This concentration can be controlled by using a medium having a controlled portion of an ingredient which does not diffuse and of another ingredient which does not produce compression stresses.
  • This expedient is particularly useful during the first ion exchange for preventing the smaller-diameter ions from penetrating too deeply into the glass.
  • lithium ions are introduced into sodium or potassium glass, one may use, for treating the glass, a medium of molten sodium salts and lithium salts, the latter being present in a small proportion.
  • the medium used for the second ion exchange treatment could, like the first, be liquid or gaseous.
  • the medium for the secondion exchange treatment could be one or more molten salts or a solution delivered to the drawing rollers of the drawing machine. If the glass carries a solidified film of the medium from the first treatment, this film coating will serve, to a certain extent, to inhibit the diffusion of the larger-diameter ions when the treatment zone for the second ion exchange is reached.
  • the adherent film could be removed before this second ion exchange occurs in order to permit the larger-diameter ions (which exchange) to penetrate still more deeply into the glass.
  • the solvent could be applied by means of rollers situated in the drawing chamber, the rollers being impregnated with solvent.
  • the glass ribbon is drawn rather rapidly and the successive portions of the ribbon each remain in the drawing chamber only two to five minutes. During this time the glass ribbon can cool substantially. For example, its temperature may drop from 500 to C. Under these conditions,
  • the larger-diameter ions will not penetrate into the glass to a sufficient extent to prevent the glass from being able to be cut into sheets upon leaving the machine, even if the diffusion of the larger-diameter ions into the glass has not been inhibited by the presence of a film coating on the ribbon.
  • the diffusion of the largediameter ions toward the internal layers of the glass can, in certain cases, continue to be produced after the glass sheet has left the drawing machine and it has been observed that the glass ribbon can still be out even some time after having left the drawing machine.
  • the distribution of the smaller-diameter ions through a transverse cross section of the glass could be rendered more uniform if the internal layers of the glass were heated, for example to a temperature above the annealing point (corresponding to a viscosity of 10""- poises) while the surface layers are maintained at a temperature inferior to the annealing point in order to prevent the occurrence of stress relaxation.
  • the glass body thus treated according to the invention is not necessarily in the form of a glass sheet, but
  • the internal heating could be carried out by exposing the glass body to a thermal radiation a large proportion of which penetrates into the interior layers of the glass while the glass body is in contact with a gaseous medium which is maintained at a temperature below the annealing point of the glass.
  • Suitable thermal radiation sources could be constituted by electric resistance heaters or members whose surfaces are heated to incandescence by the combustion of a gas.
  • the spectral composition of the thermal radiation should be so chosen with respect to the composition of the glass body to be treated that the appropriate radiation will be absorbed by the interior layers of the glass.
  • radiant heating elements will rapidly heat the internal layers of a sheet of drawn soda-lime glass if the elements are at a temperature of 1,200C or higher.
  • the radiant heat source or sources utilized can be placed in a treatment chamber through which is circulated the gaseous medium for maintaining the surfaces of the glass body at a suitable temperature.
  • the thermal treatment is evidently influenced not only by the temperature conditions but also by the duration of the exposure of the glass to the radiation.
  • Any film which adheres to the glass is preferably removed prior to the above-described internal heating procedure.
  • An article fabricated according to the present invention can be subsequently subjected to a complementary chemical tempering treatment of the low-temperature type. For example, this could be achieved by heating the article and by then replacing certain ions then present in the glass with larger-diameter ions, this being effectuated at a temperature below the annealing point of the glass.
  • This complementary chemical tempering could be effectuated whether or not a second ion exchange had been performed during the cooling of the article in the course of the primary forming operation and whether or not the article had been subjected to an internal heating of the type described above.
  • vitreous materials formed from vitrifiable mixtures containing at least one oxide or other compound of at least one element selected from the group consisting of Si, B and P, examples of such compounds being SiO B 0 and P 0 Use can also be made of vitrifiable mixtures containing at least one compound selected from the group consisting of A5 0 6e0 GeS and TiO Use can even be made of chalcogenide glasses.
  • This apparatus essentially includes shaping means for subjecting the glass to a primary forming operation while it remains in its molten or softened state, and means associated with the shaping means for bringing the ionized medium into contact with the glass when the latter is still in the shaping means and before the glass has been formed into its final shape.
  • the invention involves apparatus of the type defined in which the forming means is a glassdrawing machine.
  • the means utilized for bringing the ionized medium into contact with the glass serves to maintain the liquid and/or gaseous ionized medium in contact with the surface of the molten glass which is flowing into and/or toward the meniscus of the drawing bath.
  • the apparatus can include means for cooling the films of the ionized medium which adhere to the glass at the meniscus or very close thereto.
  • the apparatus shown in the FIGURE includes a drawing chamber 1 delimited by refractory walls 2, 3, 4, 5, 6 and 7.
  • the wall 2 is the end wall of the drawing chamber and the wall 7 is the screen, or shut-off.
  • the suspended walls 4 and 5 extend down as far as about 1 cm below the surface of the molten glass bath 8.
  • Certain principal glass currents existing in the bath 8 are indicated by the arrows and include a forward current 9 feeding the rear portion 10 of the drawn glass sheet 11 and a forward current 12 which flows under the drawing bar 15. Beyond the bar 15, three secondary currents 12', 12' and 12" branch offfrom the current 12 and supply glass for the front portion 13 of the drawn glass ribbon. The remainder of current 12 flows downwardly and forms the colder return current 17.
  • the glass which is drawn upwardly from the bath 8 forms a meniscus 18 along which the thickness of the glass is reduced as the glass is drawn upwardly.
  • the thickness of the glass at the apex of the meniscus is nearly, but not completely, equal to the final thickness of the drawn glass ribbon 11'.
  • the ribbon is drawn upwardly through the drawing chamber whose upper portion is delimited by inclined walls 20 and catch pans 21.
  • the ribbon then passes through the section 22 of the machine in which are disposed successive pairs of drawing rollers 23.
  • the surfaces of the glass drawn through the drawing chamber are cooled by coolers 24.
  • compartment 25 Between the walls 2, 3 and 4 and the surface of bath 8 is disposed a compartment 25, while a similar compartment 26 is delimited above the bath by the walls 5, 6 and 7. This latter compartment 26 is supplied with U 80, vapors.
  • the molten glass directly exposed to the vapors in compartment 26 is at a temperature of 1,080C, while the glass directly below compartment 25 is at a temperature of 1,050C.
  • the shallow spaces 27 and 28 situated above the surface of the bath in'the drawing chamber in front of and behind, respectively, the meniscus 18 are separated from the upper portions of the drawing chamber by walls 29 and 30, respectively, made of inoxidizable material.
  • the height of the walls 29 and 30 above the bath can be adjusted by any suitable means (not shown). Tubes 31 extend into the spaces 27 and 28.
  • Layers 32 and '33 of molten salt are provided to float upon the surface of bath '8 in the region below walls 29 and 30, respectively, in such a way as to communicate with the spaces 27 and 28, respectively.
  • a heat exchange fluid is caused to circulate through these spaces for maintaining the molten salt layers at a predetermined constant temperature.
  • These molten salt layers may, for example, have a thickness of the order of3 cm and the following composition, by weight:
  • the temperature of the glass in contact with the layer 32 decreases in a direction toward the meniscus from a value of 1,050C to a value of 900C, while the temperature of the glass in contact with the layer 33 similarly decreases toward the meniscus from a value of l,080C to a value of 900C.
  • rollers 40 and 41 made of porous asbestos. These rollers are fed, by conduits 42 and 43, respectively, with a mixture of molten salts composed of KNO and KNO The rollers 40 and 41 are driven at the same surface velocity as the drawing rollers.
  • coolers 44 and 45 are provided at the inner ends of the walls 29 and 30 at the inner ends of the walls 29 and 30 at the inner ends of the walls 29 and 30.
  • the quantities of salt present in the compartment 26 and in the layers 32 and 33 are preferably replenished in a continuous manner.
  • the film's of salt which adhere to the surfaces of the drawn glass when it rises in the meniscus are solidified by the coolers 44 and 45 and these coolers also reduce the temperature of the surface layers of the glass in the meniscus down to a relatively low value. Because of the cooling of these thin layers, the ion exchange between the salt and the glass ceases practically completely by the time the glass reaches the level of the meniscus apex 19.
  • the glass ribbon When passing between the rollers 40 and 41, the glass ribbon is brought into contact with the potassium salts and the potassium ions deriving from these salts diffuse into the glass.
  • the potassium ions had penetrated into the glass down to a depth of several microns from each surface of the glass ribbon. Depending on the temperature of the rollers and on the drawing speed, this depth ranges from 3 microns to 20 microns.
  • potassium salts had been brought into contact with a glass ribbon which was identical with the one described above and which had been fabricated under identical conditions, with the exception that it had not been first subjected to a penetration of lithium ions, the potassium ions would not have penetrated into the glass to a depth of greater than 2 microns and the potassium ion concentration gradient would, as a result, have been much higher.
  • potassium ions replaced 5 percent of the sodium ions initially present in the glass surface. The concentrations of both sodium and lithium ions at the interior of the glass were found to be changed by a small amount solely as a result of the second ion exchange process.
  • a sample of this tempered glass was exposed to thermal radiation after having been washed and the internal layers of the glass were maintained for 30 minutes at a temperature of 600C, i.e. at a temperature well above the annealing point of the glass (the annealing point of this glass being 540C).
  • the glass was maintained in a gas current in such a manner that its surfaces were maintained at a temperature below the annealing point. The glass was then cooled at the end of this treatment.
  • the final glass article was very similar to an article which is fabricated starting with a sodium-lithium glass which is strongly chemically tempered by the introduction of potassium and sodium ions into the surface layers of the glass.
  • a sample of the glass which had thus been treated was subjected to a low-temperature chemical tempering which was effectuated by immersing the glass in a bath of molten potassium nitrate in order to cause potassium ions to penetrate into the glass.
  • the potassium ions then penetrated into the glass sheet down to a depth of 100 microns from each surface and mainly replaced lithium ions.
  • the resulting glass was very strongly tempered and could not be cut.
  • compositions A, B and C of vitrifiable materials utilized for the manufacture of tempered glass sheets by processes according to the invention which are similar to that described above.
  • percentage of each ingredient is, by weight:
  • a B C SiO 70% 72% 64% Na,0 12% l 1% l 1% C210 6% 6% 6% MgO 7% 6% 6% rep, traces 8,0, 8% Al,0, 5% 5%
  • the tensile strength of the disk thus obtained was 12 times as large as the strength of a disk of same composition but not treated.
  • the glass is cooled without subsequent ion exchanges. It can very easily be cut and the tensile strength is three times as large as the strength of a not treated control sheet.
  • a process as defined in claim 1 wherein the ionized medium is present on the glass in the form ofa film during at least part of the time when a diffusion of smaller ions into the glass occurs, and comprising the further step of removing such film before the beginning of the second ion exchange.
  • a process as defined in claim 1 wherein the primary forming operation is constituted by a glassdrawing operation. and comprising the further step of cutting the drawn glass into sheets within a few minutes after the start of the diffusion of smaller ions into the glass.
  • a process for fabricating a tempered glass article which process includes carrying out a primary forming operation, the improvement comprising (a) bringing the glass, while it is still in the molten or softened state during the primary forming operation, into contact with an ionized medium constituting a source of exchangeable ions which are of smaller diameter than at least one type of exchangeable ions initially present in the glass, (b) permitting the smaller exchangeable ions from the medium to diffuse into the glass, in regions which will constitute surface layers of the resulting article, in exchange for such exchangeable ions initially present in the glass, such diffusion occurring before the glass has assumed its final form, (c) exposing the resulting article to thermal radiation and controlling the temperature of the article surfaces so as to cause the temperature of the interior layers of the article to be raised while the surface layers thereof are maintained at a temperature below the annealing point of the glass, and (d) controlling the heating of the internal and surface layers for causing the smaller ions which had diffused into the glass to migrate toward the interior layers of the article which are furth
  • a process according to claim 1 for forming molten or softened glass into a shaped article which process includes carrying out a primary forming operation, the improvement comprising (a) bringing the glass, while it is still in the molten or softened state during the primary forming operation, into contact with an ionized medium constituting a source of exchangeable ions which are of smaller diameter than at least one type of exchangeable ions initially present in the glass, (b) permitting the smaller exchangeable ions from the medium to diffuse into the glass, in regions which will constitute surface layers of the resulting article, in exchange for such exchangeable ions initially present in the glass, such diffusion occurring before the glass has assumed its final form, (c) reheating the article, (d) contacting the article with a medium constituting a soure of ions of larger diameter than ions present in the glass, and (e) causing the larger-diameter ions to replace such ions in the glass.
  • a process as defined in claim 15 wherein the larger-diameter ions are potassium ions and the ions which they replace are lithium ions or lithium and sodium ions.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • Surface Treatment Of Glass (AREA)
US00723360A 1967-04-25 1968-04-23 Fabrication and chemical tempering of vitreous products Expired - Lifetime US3773487A (en)

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LU53508 1967-04-25
FR146619A FR1589397A (ru) 1967-04-25 1968-03-29

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AT (1) AT291456B (ru)
BE (1) BE713603A (ru)
BG (1) BG15054A3 (ru)
CA (1) CA924506A (ru)
CH (1) CH501563A (ru)
DE (1) DE1771238A1 (ru)
ES (1) ES353129A1 (ru)
FR (1) FR1589397A (ru)
GB (1) GB1216273A (ru)
IL (1) IL29854A (ru)
NL (1) NL6805620A (ru)
SE (1) SE337660B (ru)
SU (1) SU374806A3 (ru)

Cited By (9)

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US3957476A (en) * 1970-08-04 1976-05-18 Heraeus-Schott Quarzschmelze Gmbh Method of diffusing ions into quartz glass
US4017291A (en) * 1975-06-16 1977-04-12 Jenaer Glaswerk Schott & Gen. Process for the treatment of glass by metal migration
US5114453A (en) * 1985-01-22 1992-05-19 Schott Glaswerke Lightwave guide produced by ion exchange of cs+ ions
US20070111042A1 (en) * 2005-11-16 2007-05-17 Seagate Technology Llc Alkali-depleted glass & glass-based substrates for magnetic & magneto-optical recording media
US20080082042A1 (en) * 2001-11-21 2008-04-03 Weston Medical Limited Needleless Injector Drug Capsule and a Method for Filling Thereof
US20090142484A1 (en) * 2005-03-31 2009-06-04 Hoya Corporation Method of manufacturing magnetic-disk glass substrate and method of manufacturing magnetic disk
US8141388B2 (en) * 2010-05-26 2012-03-27 Corning Incorporated Radiation collimator for infrared heating and/or cooling of a moving glass sheet
US20120210749A1 (en) * 2011-02-22 2012-08-23 Jiangwei Feng Ion exchange using nitrates and nitrites to prevent optical degradation of glass
CN107673585A (zh) * 2017-11-16 2018-02-09 海南中航特玻科技有限公司 一种3d玻璃打印机及打印方法

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US3218220A (en) * 1964-11-20 1965-11-16 Brockway Glass Co Inc Strengthened glass article and method of producing same
US3287201A (en) * 1963-01-07 1966-11-22 Pittsburgh Plate Glass Co Method of strengthening glass by ion exchange and article made therefrom
US3393987A (en) * 1962-07-27 1968-07-23 Glaverbel Method of and apparatus for protecting sheet glass during the thermal treatment thereof
US3395998A (en) * 1964-12-18 1968-08-06 Corning Glass Works Method for production of glass article having increased mechanical strength
US3410673A (en) * 1964-01-31 1968-11-12 Corning Glass Works Double ion exchange method for making glass article
US3505047A (en) * 1965-05-06 1970-04-07 Glaverbel Process and apparatus for electrochemically modification of glass

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3393987A (en) * 1962-07-27 1968-07-23 Glaverbel Method of and apparatus for protecting sheet glass during the thermal treatment thereof
US3287201A (en) * 1963-01-07 1966-11-22 Pittsburgh Plate Glass Co Method of strengthening glass by ion exchange and article made therefrom
US3410673A (en) * 1964-01-31 1968-11-12 Corning Glass Works Double ion exchange method for making glass article
US3218220A (en) * 1964-11-20 1965-11-16 Brockway Glass Co Inc Strengthened glass article and method of producing same
US3395998A (en) * 1964-12-18 1968-08-06 Corning Glass Works Method for production of glass article having increased mechanical strength
US3505047A (en) * 1965-05-06 1970-04-07 Glaverbel Process and apparatus for electrochemically modification of glass

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957476A (en) * 1970-08-04 1976-05-18 Heraeus-Schott Quarzschmelze Gmbh Method of diffusing ions into quartz glass
US4017291A (en) * 1975-06-16 1977-04-12 Jenaer Glaswerk Schott & Gen. Process for the treatment of glass by metal migration
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Publication number Publication date
CA924506A (en) 1973-04-17
IL29854A0 (en) 1968-06-20
DE1771238A1 (de) 1971-12-23
SU374806A3 (ru) 1973-03-20
GB1216273A (en) 1970-12-16
BE713603A (ru) 1968-10-14
FR1589397A (ru) 1970-03-31
BG15054A3 (bg) 1975-03-03
CH501563A (fr) 1971-01-15
IL29854A (en) 1974-05-16
NL6805620A (ru) 1968-10-28
AT291456B (de) 1971-07-12
SE337660B (ru) 1971-08-16
ES353129A1 (es) 1970-01-16

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